WO2022098528A1 - Filtres nanofibreux auto-décontaminants - Google Patents

Filtres nanofibreux auto-décontaminants Download PDF

Info

Publication number
WO2022098528A1
WO2022098528A1 PCT/US2021/056434 US2021056434W WO2022098528A1 WO 2022098528 A1 WO2022098528 A1 WO 2022098528A1 US 2021056434 W US2021056434 W US 2021056434W WO 2022098528 A1 WO2022098528 A1 WO 2022098528A1
Authority
WO
WIPO (PCT)
Prior art keywords
filter
uio
pqdmaema
pan
bacteria
Prior art date
Application number
PCT/US2021/056434
Other languages
English (en)
Inventor
Weining Wang
Zan ZHU
Ping Xu
Original Assignee
Virginia Commonwealth University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Virginia Commonwealth University filed Critical Virginia Commonwealth University
Priority to US18/251,585 priority Critical patent/US20240001270A1/en
Publication of WO2022098528A1 publication Critical patent/WO2022098528A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/10—Filter screens essentially made of metal
    • B01D39/12—Filter screens essentially made of metal of wire gauze; of knitted wire; of expanded metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1669—Cellular material
    • B01D39/1676—Cellular material of synthetic origin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2027—Metallic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2027—Metallic material
    • B01D39/2051—Metallic foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
    • B01J20/3219—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond involving a particular spacer or linking group, e.g. for attaching an active group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/327—Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B23/00—Filters for breathing-protection purposes
    • A62B23/02—Filters for breathing-protection purposes for respirators
    • A62B23/025—Filters for breathing-protection purposes for respirators the filter having substantially the shape of a mask
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
    • B01D2239/025—Types of fibres, filaments or particles, self-supporting or supported materials comprising nanofibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
    • B01D2239/0258—Types of fibres, filaments or particles, self-supporting or supported materials comprising nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0442—Antimicrobial, antibacterial, antifungal additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0471—Surface coating material
    • B01D2239/0478—Surface coating material on a layer of the filter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/0604—Arrangement of the fibres in the filtering material
    • B01D2239/0627—Spun-bonded
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/0604—Arrangement of the fibres in the filtering material
    • B01D2239/0631—Electro-spun
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/065—More than one layer present in the filtering material
    • B01D2239/0654—Support layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/10—Filtering material manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12—Special parameters characterising the filtering material
    • B01D2239/1233—Fibre diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12—Special parameters characterising the filtering material
    • B01D2239/1241—Particle diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12—Special parameters characterising the filtering material
    • B01D2239/1291—Other parameters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
    • B01D46/0028—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions provided with antibacterial or antifungal means

Definitions

  • the invention is generally related to an electrospun filter having antibacterial activity.
  • the filter includes metal-organic framework (MOF) particles modified with quaternary ammonium compounds coated on the surface of polymer nanofibers.
  • MOF metal-organic framework
  • HAIs Hospital-acquired infections
  • PM particulate matter
  • Electrospinning producing nanofibers from a polymer solution is an efficient technique to fabricate filter media with high PM filtration performance, attributing to the small diameters of the nanofibers and fiber charges.
  • MOFs metalorganic frameworks
  • a class of porous crystalline polymers have been embedded into the electrospun polymer to form the MOF-based filters.
  • the MOF-based nanofiber filters Endorsed by the hierarchical structures and tunable surface chemistry, the MOF-based nanofiber filters not only possess different functionalities but also achieve a high PM filtration efficiency and a lower pressure drop[18, 24] which is beneficial to the wearer’s comfort in breathing.
  • most of these MOF-based filters cannot be used to actively kill microorganisms such as bacteria.
  • the key is to develop a fabrication method for filters with high efficiency for the simultaneous removal of PM and inactivation of bacteria.
  • Bacteria pathogens are one of the major infectious agents that cause the persistence of HAIs.[25] Indirect contact with contaminated surfaces and airborne droplets are two of the most common modes of bacteria transmission. [26] Most commercial face masks and electrospun MOF-based filters can only passively block the transmission of airborne bacteria but not be able to kill them in-situ, i.e., on the mask surface. The bacteria being captured by the face mask may accumulate on the mask surface and can still survive for hours or even days, which would significantly increase the possibility of HAIs through surface contact transmission. [27, 28] Therefore, there is an urgent demand to develop antibacterial filters for face masks. This need can be achieved by incorporating antibacterial materials into face mask filters.
  • Quaternary ammonium compounds are potent antimicrobials that are widely used as disinfectants because of their low toxicity, the flexibility of molecule structures, the readiness of fixation on the surface, the low probability of antibiotic resistance, and so on.[35- 38]
  • the bactericidal activity of QACs stems from the electrostatic attraction between permanent positively charged nitrogen (N + ) in QACs and negatively charged bacterial membrane, [39] which would ultimately lead to cell lysis, namely the burst of cytoplasmic material.
  • the polymeric QACs with long alkyl chains exhibited enhanced bactericidal activity because the longer alky chains can interact with the lipid cell walls more strongly and destabilize the bacterial membrane more effectively.
  • Described herein is the incorporation of a QAC-modified MOF into electrospun fibers to form an active composite filter.
  • An aspect of the disclosure provides a filter comprising at least one layer of polymer nanofibers and antibacterial particles positioned on or within the at least one layer of polymer nanofibers, wherein the antibacterial particles comprise a QAC such as poly [2- (dimethyl decyl ammonium) ethyl methacrylate] (PQDMAEMA) grafted onto a surface of a MOF.
  • QAC such as poly [2- (dimethyl decyl ammonium) ethyl methacrylate]
  • the at least one layer of polymer nanofibers comprises polyacrylonitrile (PAN) nanofibers.
  • the metal-organic framework is a water-stable MOF. Typical examples include but are not limited to zirconium-based, titanium- based, or aluminum-based MOFs.
  • the filter further comprises graphitic carbon nitride (g-C N4) arranged on a surface of the MOF.
  • the antibacterial particles constitute 55-65 wt% of the filter.
  • the antibacterial particles have a larger diameter than the polymer nanofibers.
  • the antibacterial particles have an average diameter of 200-250 nm.
  • the polymer nanofibers have an average diameter of 100-150 nm.
  • the antibacterial particles are positioned on a surface of the polymer nanofibers.
  • Another aspect of the disclosure provides a face mask wearable by a subject comprising a filter as described herein.
  • Another aspect of the disclosure provides a method for decontaminating a fluid comprising bringing the fluid in contact with a filter as described herein.
  • the fluid is or comprises air.
  • the fluid is or comprises water.
  • the filter is incorporated within a face mask wearable by a subject.
  • the filter is incorporated within a heating, ventilation, and air conditioning (HVAC) system.
  • HVAC heating, ventilation, and air conditioning
  • Another aspect of the disclosure provides a method of manufacturing a filter as described herein comprising electrospinning a polymer solution comprising the antibacterial particles onto a collector. In some embodiments, the electrospinning step is performed at a temperature of 45-55°C.
  • the electrospinning step is performed at a relative humidity of 5-15%. In some embodiments, the electrospinning step is performed at a voltage of 15-20 kV.
  • the polymer solution contains polyacrylonitrile (PAN). In some embodiments, the polymer solution contains 55-65 wt% antibacterial particles.
  • FIG. 1 Schematic illustration of UiO-PQDMAEMA@PAN filter towards PM capture and airborne bacteria inactivation.
  • FIG. 1 Schematic preparation route for UiO-PQDMAEMA.
  • Figures 3A-B Schematic diagram of the experimental setup for (A) particle filtration measurements and (B) bacteria filtration tests.
  • FIGS 4A-I FT-IR spectra (A) and XRD patterns (B), high-resolution N Is XPS spectra (C), SEM images (D, E, F), and TEM images (G, H, I) of UiO-66-NH 2 , UiO-66-BIBB, and UiO-PQDMAEMA, respectively (top to bottom).
  • FIGS 5A-F SEM images, fiber diameter distribution, and BET analysis of pure PAN filter (A, C, E, F) and UiO-PQDMAEMA @ PAN filter (B, D, E, F).
  • FIGS 6A-D Digital images of as-synthesized UiO-PQDMAEMA @ PAN filter (A) and commercial N95 respirator (B); Inset image is a relatively flat sheet cut out from the commercial N95 respirator for particle filtration test; Particle filtration efficiency (C) and quality factor (D) tested by NaCl particles of 20-500 nm at a face velocity at 9.3 cm/s towards pure PAN filter, UiO-PQDMAEMA @ PAN filter, and commercial N95 respirator.
  • C particle filtration efficiency
  • D quality factor
  • FIGS 7A-B Collected S. epidermidis (A) and E. coli (B) concentration in the SKC BioSampler after the airborne bacteria passing through the UiO-PQDMAEMA @ PAN filter and commercial N95 respirator.
  • FIGS 8A-B S. epidermidis (A) and E. coli. (B) inactivation performance towards commercial N95 respirator filter, PAN, UiO-66-NH2@PAN, and UiO-PQDMAEMA @ PAN filter.
  • Figures 9A-D SEM images of UiO-PQDMAEMA@PAN filter with S. epidermidis (A, B) and E. coli. (C, D) after contacting treatment for 0 and 2 hours.
  • Figure 10 Schematic preparation route for g-C3N4@MIL-125-QAC.
  • FIGS 11A-B S. epidermidis (A) and E. coli. (B) inactivation performance after contact with C-M or C-M-Q.
  • Embodiments of the disclosure provide nanofibrous filters having antibacterial activity.
  • a layer of polymeric quaternary ammonium compounds (QAC) is added to a metal-organic framework (MOF) through a classical atomic transfer radical polymerization (ATRP) approach.
  • MOF-QAC metal-organic framework
  • ATRP classical atomic transfer radical polymerization
  • the as-synthesized active composite MOF-QAC may be embedded with a polymer solution to produce an antibacterial nanofibrous filter, which also exhibits a high PM filtration performance comparable to a commercial N95 respirator.
  • the filters described herein are capable of efficiently killing both Gram-positive and Gram-negative bacteria by destroying their cell membranes.
  • the antibacterial filters may be incorporated into face masks or used for the fabrication of heating, ventilation, and air conditioning (HVAC) air filters or for waterborne bacteria disinfection.
  • HVAC heating, ventilation, and air conditioning
  • Quaternary ammonium compounds are positively charged polyatomic ions of the structure NR + 4, R being an alkyl group or an aryl group.
  • QACs are cationic surfactants (surface active agents) that combine bactericidal and virucidal activity.
  • Examples include poly [2-(dimethyl decyl ammonium)ethyl methacrylate] (PQDMAEMA), hexadecyltrimethylammonium (‘cetrimide’), chlorhexidine, benzalkonium chloride, poly [2- tert-Butylamino ethyl methacrylate] (PTBAEMA), and poly(3-(trimethoxysilyl)propyl methacrylate) (PTMSPMA).
  • PQDMAEMA poly [2-(dimethyl decyl ammonium)ethyl methacrylate]
  • cetrimide hexadecyltrimethylammonium
  • chlorhexidine chlorhexidine
  • benzalkonium chloride poly [2- tert-Butylamino ethyl methacrylate]
  • PTMSPMA poly(3-(trimethoxysilyl)propyl methacrylate)
  • embodiments of the disclosure provide for the use of polymeric QAC which is grafted on the MOF crystals via covalent bonding which maintains the antimicrobial activity of QAC without causing leaking issues.
  • Metal-organic frameworks are a class of compounds composed of metal ions or clusters coordinated to organic ligands to form one-, two-, or three-dimensional structures. They are a subclass of coordination polymers, with the special feature that they are often porous.
  • the MOF is a water-stable MOF which generally has strong coordination bonds or great steric hindrance to prevent hydrolysis reactions (e.g. see [82]).
  • the MOF comprises an amine group.
  • the amino-derived MOFs provide a great platform to covalently attach functional groups by post-synthetic modification.
  • Exemplary MOFs include a zirconium-based MOF (e.g.
  • UiO-66-NH2 also known as 2- aminoterephthalate;oxygen(2-);zirconium(4+);tetrahydroxide
  • a titanium-based MOF e.g. MIL-125-NH2 also known as 2-aminoterephthalate;oxygen(2-);titanium;titanium (4+) ; tetrahydroxide
  • Aluminum-based MOF e.g., MIL-53-NH2, also known as 2- aminoterephthalate;oxygen(2-);aluminum;aluminum(3-i-);dihydroxide) among others.
  • the antibacterial particles may further comprise additional antibacterial agents such as a graphitic carbon nitride (g-C N4) arranged on a surface of the MOF.
  • a graphitic carbon nitride g-C N4
  • Graphitic carbon nitride g-C3N4 is a family of carbon nitride compounds with a general formula near to C3N4 (albeit typically with non- zero amounts of hydrogen) and two major substructures based on heptazine and poly(triazine imide) units.
  • Graphitic carbon nitride can be made by polymerization of cyanamide, dicyandiamide or melamine.
  • Embodiments of the disclosure further provide methods of manufacturing a filter as described herein.
  • the antibacterial particles are added to a fiber-forming polymer which is electrospun into a filter having at least one layer of polymer nanofibers where the antibacterial particles are positioned on or within the at least one layer of polymer nanofibers.
  • Electrospinning is a method to produce ultrafine (in nanometers) fibers by charging and ejecting a polymer melt or solution through a spinneret under a high-voltage electric field and to solidify or coagulate it to form a filament.
  • Suitable polymers include, but are not limited to: both organic and inorganic polymers such as polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), polycaprolactone (PCL), poly- alpha-hydroxyesters, e.g., poly-lactic-glycolic acid (PLGA), poly-lactic acid (PLA), poly- glycolic acid (PGA), other aliphatic polyesters such as glycol-type polyesters of dibasic aliphatic diacids, aromatic polyesters such as glycol-type polyesters of dibasic aromatic acids (terephthalate, etc.) polyvinyl alcohol (PVA), polyethylene oxide (PEG), or polyolefins such as polyethylene, polypropylene, polyethylene/polypropylene copolymers, polystyrene (PS), and the like; or the fiber-forming substances can be natural materials such as cellulose, chitosan, alginate, gelatin, and the like; or mixtures or blends thereof.
  • PAN
  • a solution comprising the polymer and the antibacterial particles can be delivered at a constant rate via a syringe pump; through a syringe fitted with a stainless steel blunt tip needle.
  • the needle is charged through a high voltage supply, and the resulting polymer fibers are collected on a grounded target to form a fibrous mat having antimicrobial properties.
  • the electrospinning step is performed at a temperature of about 40-60°C, e.g. about 45-55 °C. In some embodiments, the electrospinning step is performed at a relative humidity of about 5- 20%, e.g. about 5-15%. In some embodiments, the electrospinning step is performed at a voltage of about 10-25 kV, e.g. about 15-20 kV. In some embodiments, the antibacterial particles constitute about 50-70 wt%, e.g. about 55-65 wt% of the electrospun filter.
  • Multi-layer mats may be produced with each layer having the same or different physical properties (i.e. thickness, porosity, etc.) and/or the same or different antimicrobial particles.
  • the layers may be electrospun separately and then combined, or a subsequent layer or layers may be electrospun directly onto a first layer.
  • the antibacterial particles are exposed on the surface of the polymer fibers.
  • the antibacterial particles are configured to have a larger diameter than the polymer nanofibers.
  • the antibacterial particles have an average diameter of about 175-275 nm, e.g. about 200-250 nm.
  • the polymer nanofibers have an average diameter of about 75-175 nm, e.g. about 100-150 nm.
  • Embodiments of the disclosure also provide a face mask incorporating a filter as described herein.
  • Suitable masks and respirators (herein referred to collectively as “face masks” or “masks”) are known in the art.
  • Face masks include both disposable and non-disposable masks and include masks that can be reused and washed.
  • a face mask of the disclosure includes those that cover a wearer’s nose and/or mouth, and even preferably, a portion of the wearer's face, i.e., cheeks, jaw, chin, and so forth.
  • a mask/respirator is an N-95, N-99, N-100, R-95, R-99, R-100, P-95, P-99, or P-100 respirator.
  • Suitable masks may also include a bendable metal reinforcement nose bar to allow custom fitting of the mask around the nose of a wearer.
  • Suitable masks may utilize ear loops or may have straps that are configured to wrap around a wearer’s head.
  • the QAC-modified MOF filter forms the entirety of the face-covering portion of the face mask without any additional layers.
  • the QAC-modified MOF filter is arranged on top (on an outer surface) of a conventional mask.
  • the QAC-modified MOF filter is arranged between two support protection layers, such as spun-bond polypropylene (PP) fabric.
  • PP polypropylene
  • a filter as described herein may have a shape and size such that it is configured to be inserted into the filter pocket of a commercially available face mask.
  • the filter may be square or rectangular in shape.
  • the filter may have a length or width of about 5-15 cm.
  • Each individual layer of the filter may have a thickness of 10-50 pm.
  • the fibers are nonwoven.
  • the density of the fiber materials (p) is 0.2-0.6 g/cm 3 .
  • the packing density (a) of the filter is 0.01-0.1.
  • the packing density is the ratio of the volume of the fibers to the volume of the fibrous media.
  • the antibacterial particles may be introduced as fillers in the electrospun nanofibers which enables the face mask to have an enhanced surface area and hierarchical pore size distribution.
  • the filter embedding the QAC-modified MOF crystals has a high particle filtration efficiency (>95%) with satisfactory pressure drop, which ensures comfort during breathing.
  • Further embodiments of the disclosure provide a method for decontaminating a fluid comprising bringing the fluid in contact with a filter as described herein.
  • the fluid is or comprises air or water.
  • the filter is incorporated within a heating, ventilation, and air conditioning (HVAC) system.
  • HVAC heating, ventilation, and air conditioning
  • the filter may also adsorb toxic gas molecules such as volatile organic compounds (VOCs), e.g. toluene, benzene, and styrene which may emit from tobacco smoke, traffic exposure, solvents, and other environmental sources.
  • VOCs volatile organic compounds
  • the fillers implemented in the electrospun nanofibers were constructed by grafting a layer of antibacterial polymeric quaternary ammonium compound (QAC), that is, poly [2-(dimethyl decyl ammonium)ethyl methacrylate] (PQDMAEMA), onto the surface of metal-organic framework (MOF, UiO-66-NH2 as a model) to form the active composite UiO-PQDMAEMA.
  • QAC antibacterial polymeric quaternary ammonium compound
  • MOF metal-organic framework
  • UiO-66-NH2 as a model
  • the UiO-PQDMAEMA filter demonstrates an excellent PM filtration efficiency (> 95%) at the most penetrating particle size (MPPS) of 80 nm, which is comparable to that of the commercial N95 respirators.
  • the UiO-PQDMAEMA filter is capable of efficiently killing both Gram-positive (S. epidermidi.s) and Gram-negative (E. coli) airborne bacteria.
  • Gram-positive S. epidermidi.s
  • Gram-negative E. coli
  • the strong electrostatic interactions between the anionic cell wall of the bacteria and positively charged nitrogen of UiO-PQDMAEMA are the main reasons for severe cell membrane disruption, which leads to the death of bacteria.
  • the present work provides a new avenue for combating air contamination by using the QAC-modified MOF-based active filters.
  • UiO-PQDMAEMA The synthetic procedures for UiO-PQDMAEMA preparation are schematically depicted in Figure 2.
  • the raw UiO-66-NH2 was first decorated with initiator 2- bromoisobutyryl bromide (BIBB) via covalent bonding to form UiO-66-BIBB.
  • BIBB initiator 2- bromoisobutyryl bromide
  • QDMAEMA monomer 2-(dimethyl decyl ammonium) ethyl methacrylate
  • UiO-PQDMAEMA The details of material synthesis processes are provided below.
  • the UiO-66-BIBB was obtained by functionalizing UiO-66-NH2 under the protection of nitrogen in a 50 ml flask.
  • 0.3 g UiO-66-NH2 was suspended in 20 ml anhydrous THF by sonication.
  • 418 pF TEA and 124 pF BiBB were dissolved in 10 ml THF separately.
  • the TEA solution was injected into the UiO-66-NH2 suspension under stirring.
  • the BIBB solution was dropwise added into the mixture in 30 minutes with ice water cooling and strong stirring.
  • the reactants were subsequently sealed and stirred at 50 °C for 24 hours.
  • the particles were washed with THF and methanol and dried under vacuum at 40 °C.
  • the obtained products were named UiO-66-BIBB.
  • Poly [2(dimethyl decyl ammonium) ethyl methacrylate] (PQDMAEMA) brushes were prepared by ATRP of QDMAEMA from UiO-66-BIBB.
  • QDMAEMA Poly [2(dimethyl decyl ammonium) ethyl methacrylate] brushes were prepared by ATRP of QDMAEMA from UiO-66-BIBB.
  • QDMAEMA 2.68 ml DMAEMA and 3.9 ml of 1-bromodecane were added into 10 ml acetonitrile in a 50 ml flask and reacted for 24 hours at 40 °C. After cooling to room temperature, the solution was slowly dripped into 200 ml isopropyl ether, and the white precipitates were collected by centrifugation. The precipitate was dissolved in acetonitrile and then carried on the precipitation centrifugation process for another two times.
  • the face mask filter was fabricated via the facile electrospinning method, where the electric force is generated by a high voltage to draw threads of polymer solutions to fibers with diameters in the order of hundred nanometers.
  • DMF N, N- dimethylformamide
  • PAN 6 wt % PAN loading
  • UiO-66-NH2@PAN 60 wt % MOF loading
  • UiO-PQDMAEMA @ PAN 60 wt % UiO-PQDMAEMA loading
  • Cu@PAN 60 wt % CU(NO)3- 3H2O loading
  • the electrospinning process was operated at a precursor flow rate of 0.5 ml/hour. A high voltage of 17 kV was applied and the distance between the collector and spinneret was set at 17 cm. The obtained fibers were collected on the substrate of stainless-steel mesh (from McMaster-Carr). The temperature and relative humidity (RH) were kept at 50 °C and 10%, respectively.
  • the surface functional groups of the samples were analyzed by a Fourier transform infrared (FT-IR) spectrometer (Nicolet iS50).
  • FT-IR Fourier transform infrared
  • XRD X-ray diffraction
  • Morphologies of the samples were observed by SEM (scanning electron microscopy, Su-70, Hitachi) and TEM (transmission electron microscopy, JEOL JEM-F200).
  • Thermogravimetric analysis (TGA) was conducted with a TA Q500 under nitrogen gas flow with a heating rate of 10 °C/min.
  • the gas adsorption experiments were carried out using Autosorb iQ (Quantachrome Instrument).
  • the fluorescence images were obtained by the Zeiss Axiovert 200M fluorescence microscope.
  • the surface compositions were determined by the X-ray photoelectron spectrometer (XPS, Thermo Scientific ESCALAB 250).
  • the size-fractionated penetration, P(d x ), representing the fraction of particles with diameter d x can go through the filter medium, is defined as: where C(d x ) downstream and C(d x ) upstream are the downstream and upstream number concentrations of d x particles, respectively.
  • the size-fractionated filtration efficiency, PFE d x ), of the filter is thus calculated as:
  • the correlation ratio test was performed.
  • the same particle generator as used for generating challenge aerosols for the test was turned on, but without a test filter medium in the holder.
  • the upstream and downstream samples were measured for the same sampling time internals as used in the tests.
  • the general formula for the correlation ratio, R d x ) can be calculated as: where C d x ) downstream 0 is the particle concentration with particle size d x measured at the downstream sampling location without a filter medium; C d x ) upstream 0 is the particle concentration with the particle size d x measured at the upstream sampling location without a filter medium.
  • the finally corrected PFE' (d x ) takes the following form:
  • the upstream and downstream particle concentrations were measured for at least three times to obtain the representative filtration results.
  • the standard deviation (cr(d x )) was calculated using the following equation : where a dO wnstream an d ⁇ downstream are the standard deviations at the downstream and upstream of the filter holder, respectively.
  • FIG. 3b A system for bacteria filtration tests was also developed in this study (Fig. 3b). Specifically, two representative bacteria S. epidermidis (Gram-positive) and E. coli (Gram- negative) suspensions with a density at 10 7 CFU/mL in phosphate-buffered saline (PBS) solution were used as precursors. Then, the suspensions were atomized by an ultrasonic nebulizer operated at 2.4 MHz to generate bioaerosols to challenge the filters at a flow rate of 12.5 L/min for 1 minute. A BioSampler (SKC Inc.) containing 20 ml sterile PBS solution was used to collect the escaped bioaerosol. After collection, the escaped bacteria concentrations were determined by the standard plate counting method.
  • PBS phosphate-buffered saline
  • the bacterial filtration efficiency (BFE) of the filter is defined as follows: where (CFU/ml) is the bacteria concentration in the Biosampler with a face mask filter operation; C totai (CFU/ml) is the bacteria concentration in the Biosampler without a mask filter operation.
  • the filter After being challenged by the bioaerosol for 1 minute, the filter was sealed in a petri dish and placed in the dark for 2 hours to allow the interaction between the filter surface and captured bacteria. Subsequently, the filter was vortexed at 5000 rpm for 5 minutes to resuspend the captured bacteria in the 20 ml PBS solution. Then, the suspension was diluted with PBS, and 3 pL of each decimal dilution was dropped in the sterile nutrient agar culture plates. The agar plates with the bacteria suspensions were incubated at 37 °C for 20 hours to give the visible colonies, which were enumerated to calculate the number of living bacteria.
  • the bacteria inactivation efficiency was calculated by the following equation: where C ve is the concentration of live bacteria remaining on the filter. Additionally, after being placed in the dark for 2 hours, the filter was cultured in the nutrient agar at 37 °C for 20 hours for residual analysis of remained viable cells.
  • Fluorescence microscopy is a useful technique to examine the viability of bacterial cells before and after contacting the filter.
  • 1 ml bacteria cell suspension was centrifuged and resuspended in 10 pL of PBS solution, which was subsequently stained by a live/dead staining kit (Molecular Probes, Invitrogen) in the dark for 1 hour.
  • Bacterial cells with intact cell membranes (live) were stained by SYTO 9 and fluorescent green, whereas propidium iodide (PI) penetrates only damaged membranes and stains the dead bacteria, which presented red fluorescence.
  • PI propidium iodide
  • Fig. 4c shows the deconvoluted N Is core-level peaks of UiO-66-NH2, UiO-66-BIBB, and UiO- PQDMAEMA.
  • the XPS spectra of UiO-66-NH2 and UiO-66-BIBB exhibit two nitrogen peaks at 398.9 eV and 399.8 eV, which are assigned to N-H and C-N, respectively.[55] A new peak at 402.0 eV is found in UiO-PQDMAEMA, which is attributed to the C-N + component from the monomer QDMAEMA, confirming that an outer quatemized surface layer is formed.[35] Based on the XPS spectra in Fig. 4c, the quatemization degree (QD) of UiO- PQDMAEMA was estimated to be 48%. [56]
  • UiO-66-NH2 The morphologies of UiO-66-NH2, UiO-66-BIBB, and UiO-PQDMAEMA were also observed by SEM. As shown in Figs. 4(d, e, g, h), UiO-66-BIBB has similar crystal shapes to that of UiO-66-NH2 with an average particle size of -265 nm. After the ATRP reaction, the surface of UiO-PQMAEMAEMA becomes smooth (Fig. 4f), and an obvious polymer shell can be observed in its TEM image (Fig. 4i). Understandably, the core contour and size are similar to those of unmodified UiO-66-NH2, which is well consistent with the XRD results in Fig. 4b. According to the TGA results, the percentage of polymer in UiO-PQDMAEMA was estimated at 9.93%. All the above results once again confirm the successful grafting of PQDMAEMA onto UiO-66-NH2.
  • the surface tension is also a function of temperature, which can be expressed as: [58] where y° is the constant for each liquid, n is a positive empirical factor, T c is the critical temperature and T is the actual temperature.
  • y° is the constant for each liquid
  • n is a positive empirical factor
  • T c is the critical temperature
  • T is the actual temperature.
  • the average diameter of pure PAN fibers is measured to be -139 nm (Fig. 5c), which is thinner than those fabricated at room temperature (25 °C) and higher RH of 35% with an average diameter size of 242 nm.
  • Fig. 5b shows the morphology of the UiO-PQDMAEMA@PAN filter, where the UiO- PQDAMEMA particles are well decorated on the PAN fiber surface with an overall average diameter of 368 nm (Fig. 5d).
  • the exposure of the UiO-PQDMAEMA particles to the environment gives them more contacting opportunities with captured bacteria.
  • the nitrogen sorption isotherms of the pure PAN and UiO-PQDMAEMA @ PAN filters are shown in Fig.
  • the UiO-PQDMAEMA @ PAN filter exhibits a hierarchical structure containing the characteristics of both micropores and mesopores (Fig. 5f). Moreover, XRD and FT-IR analyses indicate that the crystalline structure and surface chemistry of the UiO-PQDMAEMA are retained after the electrospinning process.
  • Fig. 6c compares the efficiency curves amongst the pure PAN, UiO-PQDMAEMA@PAN, and N95 filters. It is seen that the particle filtration efficiency decreases with particle size until it reaches the most penetrating particle size (MPPS) at around 80 nm, and subsequently increases for particles greater than 80 nm.
  • MPPS most penetrating particle size
  • the thickness of the UiO-PQDMAEMA@PAN filter is adjusted to 16 pm, and the minimum filtration efficiency of as-synthesized UiO- PQDMAEMA@PAN filter at 80 nm is measured to be -95.1%.
  • the filtration performance is comparable to that of a commercial N95 respirator, which makes the UiO- PQDMAEMA@PAN a candidate for an N95 respirator filter medium. It is noted that as compared to the pure PAN filter tested under the same pressure drop (52.3 Pa), a higher filtration efficiency is obtained for the UiO-PQDMAEMA@PAN filter.
  • the UiO-PQDMAEMA@PAN filter is endowed with hierarchical structures, which contain both micropores and mesopores by embedding the porous UiO-PQDMAEMA particles in the electrospun fibers.
  • the pressure drop is another very important parameter, as breathing air behind the face mask requires significant pressure or energy provided by the users, which is highly related to wearer’s comfort and health during breath. Therefore, a low-pressure drop is always a desirable filter property.
  • the quality factor (QF) a comprehensive parameter, is used to evaluate the filtration performance of the filter media, which takes both efficiency and pressure into account.
  • the QF is defined as: [68] ln(l - PFE)
  • the UiO-PQDMAEMA@PAN filter has a much better filtration performance because of the incorporation of UiO-PQDMAEMA in the electrospun nanofibers. Additionally, the minimum QF value of the UiO-PQDMAEMA @ PAN filter is calculated to be 0.058 at MPPS of 80 nm, which is comparable to that of 0.056 for the commercial N95 respirator at 50 nm, indicating that the UiO-PQDMAEMA@PAN filter demonstrates a satisfactory filtration performance.
  • the bacteria filtration performance of the UiO-PQDMAEMA @ PAN filter is evaluated by challenging with the bioaerosols containing S. epidermidis (Gram-positive bacteria) and E. coli (Gram-negative bacteria).
  • the schematic diagram of the experimental setup for the bioaerosol filtration is shown in Fig. 3b.
  • the BioSampler (SKC Inc) which combines impingement with centrifugal motion is used for the escaped bacteria collection. Specifically, there are three collection nozzles positioned at a specific angle above the collection sterile PBS solution during the sampling, and the air stream with bacteria is directed to the wall of the sampling where a liquid film is formed due to the centrifugal motion of the liquid.
  • the as-synthesized UiO-PQDMAEMA@PAN filter demonstrates an excellent performance towards bacteria capture, which could be used to protect user’s safety by blocking out the routes of airborne bacteria transmission.
  • the bacteria inactivation performance of the UiO-PQDAMEMA@PAN filter was also evaluated towards both S. epidermidis and E. coli. Control experiments of pure PAN filter and UiO-66-NH2@PAN filter were also conducted for comparison. As shown in Fig. 8(a, b), both pure PAN and UiO-66-NH2@PAN filters show limited capabilities of killing bacteria while the UiO-PQDMAEMA@PAN filter has a significant inactivation efficiency of -97.4% of S. epidermidis and -95.1% of E. coli, indicating that the grafted UiO-PQDMAEMA on the surface of PAN fibers enables the filter to have efficient bactericidal behaviors.
  • the ratio of live and dead bacteria in fluorescence images shows almost no change in the control group of pure PAN and UiO-66-NH2@PAN filters once again confirming the bactericidal behaviors of the UiO-PQDMAEMAM@PAN filter.
  • the commercial N95 respirator was also tested towards bactericidal performance. As shown in Fig. 8(a, b), negligible bacterial inactivation efficiencies can be obtained for S. epidermidis and E. coli, indicating that most of the adhered bacteria are still alive, which is the main reason that the contaminated respirator could be the source of HAIs transmission.
  • the as- synthesized UiO-PQDMAEMA @ PAN filter demonstrates an efficient and rapid bacteria inactivation performance, which makes it useful for the antibacterial filter in the N95 level respirator.
  • the discrepancy in the antibacterial efficiency could be caused by various cell structures between the Gram-positive bacteria and the Gram-negative bacteria.
  • the Gram-positive bacterial cell wall is composed of a simple layer of peptidoglycan. This layer has numerous pores, which allow the QAC molecules to readily penetrate the thick cell wall and reach the cytoplasmatic membrane.
  • the cell wall of the Gram-negative bacteria E. coli is comprised of two membranes reinforced by the expression of lipopolysaccharide on the cellular surface, which provides an additional protective property. [76] Therefore, a more efficient antibacterial performance was obtained towards S. epidermidis than E. coli.
  • the positive charge density of outer layer is another key parameter to define antibacterial efficacy.
  • the prerequisite charge density should be above the critical threshold of IxlO 12 -10 14 N + /cm 2 .
  • the crystal in Fig. 4i is the initial UiO-66-NH2, which is decorated by a layer of QAC polymer. Assuming that charges were uniformly distributed within the polymer layer, the charge density (CD) can be determined by the following equation:
  • UiO-PQDMAEMA was calculated to be 3xl0 14 N + /cm 2 . Therefore, UiO-PQDMAEMA in this work is expected to exhibit effective antibacterial actions.
  • the monomer DMAEMA is quatemized by 1- bromodecane to impart the QDMAEMA with 10 carbon atoms in the alkyl chains (Fig. 2).
  • the relatively long alkyl chains in UiO-PQDMAEMA could interact strongly with the peptidoglycan cell wall and, finally, bacteria are killed by the lysis of their cytoplasm.
  • the UiO-PQDMAEMA @ PAN filter demonstrated excellent bactericidal activities towards both Gram-positive S. epidermidis and Gram-negative E. coli via a contact-killing mechanism.
  • the incorporated UiO-PQDMAEMA particles with positively charged nitrogen (N + ) in the long alky chain resulted in the deformation and damage of cells after electrostatic interactions between UiO-PQDMAEMA and bacteria.
  • N + positively charged nitrogen
  • the current work indicates that the UiO-PQDMAEMA @ PAN is a comprehensive protection core filter for the N95 respirator or other face masks against PM and airborne bacteria. This study also sheds light on the design of QAC modified antibacterial materials and paves a way for the application of these materials in air cleaning.
  • Graphitic carbon nitride (g-C N4) is a family of carbon nitride compounds with a general formula near to C3N4 (albeit typically with non-zero amounts of hydrogen) and two major substructures based on heptazine and poly(triazine imide) units.
  • Graphitic carbon nitride can be made by polymerization of cyanamide, dicyandiamide or melamine.
  • this composite (C-M- Q) is also able to adsorb toxic air contaminants, such as toluene.
  • C-M is an abbreviation for g-C3N4@MIL-125-NH2, which is the foundation for the improved antibacterial performance and toxic gas adsorption.
  • the as-synthesized C-M is an efficient photocatalyst, which can disinfect pathogens by radical oxygen species (ROS) generated under the light irradiation.
  • ROS radical oxygen species
  • Graphitic carbon nitride (g-C N4) was prepared as follows: 10 g urea (Sigma Aldrich, 99.0-100.5%) was put in an alumina crucible with a cover. Then, the crucible was heated to 550°C at a rate of 0.5°C/min in a muffle furnace and maintained at this temperature for 3 hours. The yellow g-C3N4 was obtained after cooling down to the room temperature.
  • g-C N4 In g-C3N4@MIL-125-NH2 (C-M), g-C N4 (C) is a very efficient visible-light- responsive photocatalyst due to its suitable electronic band structures.
  • MIL-125-NH2 M
  • MOF metal-organic framework
  • C-M-Q can also adsorb toxic gas molecules (e.g., toluene) because of the high porosity and surface area of MIL-125-NH2.
  • toxic gas molecules e.g., toluene
  • NIOSH Approval of Respiratory Protective Devices, Code of Federal Regulations Title 42, Part 84. NIOSH, Cincinnati, OH, USA., 1995, 16, 529-531.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geology (AREA)
  • Toxicology (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Filtering Materials (AREA)

Abstract

L'invention concerne un filtre ayant une activité antibactérienne. Le filtre comprend au moins une couche de nanofibres polymères et des particules antibactériennes positionnées sur ou à l'intérieur de la ou des couches de nanofibres polymères, les particules antibactériennes comprenant un composé d'ammonium quaternaire greffé sur une surface d'une structure organométallique. L'invention concerne également des procédés de fabrication du filtre et de décontamination d'un fluide.
PCT/US2021/056434 2020-11-03 2021-10-25 Filtres nanofibreux auto-décontaminants WO2022098528A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US18/251,585 US20240001270A1 (en) 2020-11-03 2021-10-25 Self-decontaminating nanofibrous filters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202063108941P 2020-11-03 2020-11-03
US63/108,941 2020-11-03

Publications (1)

Publication Number Publication Date
WO2022098528A1 true WO2022098528A1 (fr) 2022-05-12

Family

ID=81458206

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2021/056434 WO2022098528A1 (fr) 2020-11-03 2021-10-25 Filtres nanofibreux auto-décontaminants

Country Status (2)

Country Link
US (1) US20240001270A1 (fr)
WO (1) WO2022098528A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114939186A (zh) * 2022-07-10 2022-08-26 广东工业大学 一种Ti-MOF/壳聚糖支架及其制备方法与应用
WO2024013468A1 (fr) * 2022-07-11 2024-01-18 University Court Of The University Of St Andrews Réseau organo-métallique fonctionnalisée

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110174720A1 (en) * 2009-07-22 2011-07-21 Massachusetts Institute Of Technology Multifunctional Electroprocessed Membranes
US20110297609A1 (en) * 2010-06-04 2011-12-08 Jin Hu Aircraft potable water system
US20170008915A1 (en) * 2014-02-19 2017-01-12 The Regents Of The University Of California Acid, solvent, and thermal resistant metal-organic frameworks
CN107455822A (zh) * 2017-09-12 2017-12-12 江苏纳纤新材料科技有限公司 一种纳米纤维‑微米纤维复合防雾霾口罩

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110174720A1 (en) * 2009-07-22 2011-07-21 Massachusetts Institute Of Technology Multifunctional Electroprocessed Membranes
US20110297609A1 (en) * 2010-06-04 2011-12-08 Jin Hu Aircraft potable water system
US20170008915A1 (en) * 2014-02-19 2017-01-12 The Regents Of The University Of California Acid, solvent, and thermal resistant metal-organic frameworks
CN107455822A (zh) * 2017-09-12 2017-12-12 江苏纳纤新材料科技有限公司 一种纳米纤维‑微米纤维复合防雾霾口罩

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BASHARNAVAZ HADI; HABIBI-YANGJEH AZIZ; KAMALI SEYED HOSSEIN: "A first-principles study on the interaction of CO molecules with VIII transition metals-embedded graphitic carbon nitride as an excellent candidate for CO sensor", PHYSICS LETTERS A., NORTH-HOLLAND PUBLISHING CO., AMSTERDAM., NL, vol. 383, no. 21, 1 January 1900 (1900-01-01), NL , pages 2472 - 2480, XP085704416, ISSN: 0375-9601, DOI: 10.1016/j.physleta.2019.05.013 *
DIEN LI, NATALIA B SHUSTOVA 2, COREY R MARTIN 2, KATHRYN TAYLOR-PASHOW 3, JOHN C SEAMAN 4, DANIEL I KAPLAN 3, JAKE W AMOROSO 3, RO: "Anion-exchanged and quaternary ammonium functionalized MIL-101-Cr metal-organic framework (MOF) for Re04/Tc04 sequestration from groundwater", JOURNAL OF ENVIRONMENTAL RADIOACTIVITY, ELSEVIER, 1 October 2020 (2020-10-01), pages 106372, XP055939185 *
LEE HANSOL, JEON SANGMIN: "Polyacrylonitrile Nanofiber Membranes Modified with Ni-Based Conductive Metal Organic Frameworks for Air Filtration and Respiration Monitoring", ACS APPLIED NANO MATERIALS, vol. 3, no. 8, 28 August 2020 (2020-08-28), pages 8192 - 8198, XP055939188, ISSN: 2574-0970, DOI: 10.1021/acsanm.0c01619 *
ZHU ZAN, ZHANG YU, BAO LIANG, CHEN JIANPING, DUAN SHUN, CHEN SHENG-CHIEH, XU PING, WANG WEI-NING: "Self-decontaminating nanofibrous filters for efficient particulate matter removal and airborne bacteria inactivation", ENVIRONMENTAL SCIENCE: NANO, ROYAL SOCIETY OF CHEMISTRY, GB, vol. 8, no. 4, 22 April 2021 (2021-04-22), GB , pages 1081 - 1095, XP055939187, ISSN: 2051-8153, DOI: 10.1039/D0EN01230K *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114939186A (zh) * 2022-07-10 2022-08-26 广东工业大学 一种Ti-MOF/壳聚糖支架及其制备方法与应用
WO2024013468A1 (fr) * 2022-07-11 2024-01-18 University Court Of The University Of St Andrews Réseau organo-métallique fonctionnalisée

Also Published As

Publication number Publication date
US20240001270A1 (en) 2024-01-04

Similar Documents

Publication Publication Date Title
Zhu et al. Self-decontaminating nanofibrous filters for efficient particulate matter removal and airborne bacteria inactivation
He et al. Tailoring moisture electroactive Ag/Zn@ cotton coupled with electrospun PVDF/PS nanofibers for antimicrobial face masks
JP6851648B2 (ja) 表面の長期殺菌のための抗菌コーティング
Bortolassi et al. Efficient nanoparticles removal and bactericidal action of electrospun nanofibers membranes for air filtration
Armentano et al. Polymer materials for respiratory protection: processing, end use, and testing methods
US20240001270A1 (en) Self-decontaminating nanofibrous filters
US20100040655A1 (en) Anti-viral Formulations Nanomaterials And Nanoparticles
Blosi et al. Polyvinyl alcohol/silver electrospun nanofibers: biocidal filter media capturing virus‐size particles
Mallakpour et al. Fabrication of air filters with advanced filtration performance for removal of viral aerosols and control the spread of COVID-19
JP2008188082A (ja) マスク
Tian et al. Polycaprolactone nanofiber membrane modified with halloysite and ZnO for anti-bacterial and air filtration
WO2010120730A1 (fr) Matériaux, appareil et procédés éliminant des substances dangereuses
Dahanayake et al. Recent breakthroughs in nanostructured antiviral coating and filtration materials: a brief review
Cui et al. Preparation of PAN/SiO2/CTAB electrospun nanofibrous membranes for highly efficient air filtration and sterilization
WO2022255885A1 (fr) Filtres contenant des nanofibres chargées de terpène pour une activité bactéricide, fongicide et virucide améliorée, leurs procédés de préparation et leurs applications
Lim et al. Electrospray-on-Electrospun breathable, biodegradable, and robust nanofibrous membranes with photocatalytic bactericidal activity
Natsathaporn et al. Functional fiber membranes with antibacterial properties for face masks
Yao et al. A hierarchical structure of flower-like zinc oxide and poly (vinyl alcohol-co-ethylene) nanofiber hybrid membranes for high-performance air filters
Wang et al. Polarity-dominated chitosan biguanide hydrochloride-based nanofibrous membrane with antibacterial activity for long-lasting air filtration
WO2021158726A1 (fr) Milieux de filtration d'air ayant des agglomérats de nanoparticules métalliques adhérant à ceux-ci, formation de ceux-ci et utilisation de ceux-ci
Wang et al. Reusable electrospun nanofibrous membranes with antibacterial activity for air filtration
US11678703B2 (en) Coated substrates and articles with anti-viral properties, and fabrication processes
Yoon et al. A capture and inactivation system against pathogens in indoor air using copper nanoparticle decorated melamine sponge hybrid air filters
Gogoi et al. Nanometer-Thick Superhydrophobic Coating Renders Cloth Mask Potentially Effective against Aerosol-Driven Infections
Chen et al. Biocompatibile nanofiber based membranes for high-efficiency filtration of nano-aerosols with low air resistance

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21889841

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21889841

Country of ref document: EP

Kind code of ref document: A1